WO2011058898A1 - Electroconductive laminate and process for production thereof - Google Patents

Abstract

An electroconductive laminate obtained by laminating an undercoat resin layer and an electroconductive layer on at least one surface of a substrate in this order from the substrate side, wherein the undercoat resin layer comprises both a urethane acrylate resin that contains a glycol skeleton and a resin that has a graft structure and contains hydrophilic groups in the side chain. A touch panel using the electroconductive laminate ensures smooth writing and exhibits high input sensitivity and high durability. Further, the electroconductive laminate is suitable for use as an electrode member in a display (such as a liquid crystal display, an organic electroluminescent device or an electronic paper), a solar cell module, or the like.

Description

Conductive laminate and manufacturing method thereof

The present invention relates to a conductive laminate having a conductive layer on a base resin layer. Further, the present invention relates to a conductive laminate suitable for electrode members used for displays such as touch panels, liquid crystal displays, organic electroluminescence, electronic paper, and solar cell modules.

In recent years, mobile phones and game machines equipped with touch panels have become widespread. A conductive member for an electrode is used for the touch panel, but fine input by a pen or the like to the touch panel has progressed, and writing quality, high input sensitivity, and durability are required for the conductive member to be used.

A conductive laminate in which a non-conductive layer surface of a substrate having a conductive layer laminated on the surface by a dry process and another substrate are bonded to each other through an adhesive layer is used for a touch panel. A conductive laminate having an adhesive layer has good writing quality and input sensitivity because the adhesive layer serves as a cushion. However, since the conductive layer is laminated by a high cost dry process and further uses a plurality of base materials, the cost is very high and it cannot be produced at low cost.

A conductive laminate in which a cushion layer is provided on a base material and a resin layer and a conductive layer are laminated in this order on the substrate is a base layer for laminating the conductive layer, even if the cushion layer is provided. Since the layer was provided, the cushion effect of the cushion layer could not be obtained.

A conductive laminate in which a resin layer, a layer having a refractive index different from that of the substrate, and a conductive layer are laminated in this order on the substrate are poor in writing quality and input sensitivity even if the multilayered layer is a thin film. It was.

In a conductive laminate in which a base layer is provided on a base material and a conductive layer is laminated thereon, the conductive laminate in which the base layer is much thinner than the base material has no cushion effect and writing quality and input sensitivity are poor. .

A conductive laminate in which the base layer is made of a polyurethane resin is known (Patent Document 1). The conductive laminate composed of the polyurethane resin for the underlayer lacked the cushion effect of the underlayer, and the writing quality and input sensitivity were poor.

A conductive laminate in which the base layer is made of a urethane acrylate resin is known (Patent Document 2). The conductive laminate comprising the base layer made of urethane acrylate resin did not have the cushion effect of the base layer, and the writing quality and input sensitivity were poor.

An electrically conductive laminate comprising a urethane acrylate resin having a glycol skeleton as an underlayer is known (Patent Document 3). If the underlying layer is only urethane acrylate resin, the hydrophilicity of the surface of the underlying resin layer is insufficient. In particular, in the case of a conductive layer using a conductive component made of a water-containing composition, unevenness and defects are formed when laminated on the base resin layer, the appearance of the conductive laminate is poor, and the surface conductivity is poor. The input sensitivity was bad.

JP 2008-243532 A JP 2007-42284 A JP 2009-302013 A

The present invention provides a conductive laminate that improves the writing quality and input sensitivity of a touch panel and has good durability.

The present invention is a conductive laminate in which a base resin layer and a conductive layer are laminated in order of a base resin layer and a conductive layer on at least one surface of the base material from the base material side, and the base resin is a urethane having a glycol skeleton. The conductive laminate is a resin containing an acrylate resin and a resin having a graft structure having a hydrophilic group in a side chain.

Furthermore, the present invention is a method for producing a conductive laminate in which a base resin layer is formed on a base material and then a conductive layer is formed on the base resin layer, wherein the base resin has a glycol skeleton side with a urethane acrylate resin. It is a manufacturing method of the electrically conductive laminated body containing resin of the graft structure which has a hydrophilic group in a chain | strand.

The touch panel using the conductive laminate of the present invention has good writing quality, high input sensitivity, and good durability.

Further, the conductive laminate of the present invention can be suitably used for display members such as liquid crystal displays, organic electroluminescence, and electronic paper, and used electrode members such as solar cell modules.

It is an example of the cross-sectional schematic diagram of the electrically conductive laminated body of this invention. It is an example of the schematic diagram of resin of the graft structure which has a hydrophilic group in the side chain of this invention. It is an example of the schematic diagram of the linear structure observed from the conductive layer side of the conductive laminated body of the present invention. It is the schematic diagram which showed an example of the touchscreen which is the one aspect | mode of this invention. Schematic diagram of fluidized bed vertical reactor

Hereinafter, the present invention will be described in more detail.

The conductive laminate of the present invention is a conductive laminate in which a base resin layer and a conductive layer are laminated in order of a base resin layer and a conductive layer from at least one surface of the base material in this order, and the base resin is glycol. The conductive laminate is a resin containing a urethane acrylate resin having a skeleton in the structure and a graft structure resin having a hydrophilic group in the side chain.

The base material in the conductive laminate of the present invention is preferably a base material having a high visible light total light transmittance, and more preferably a transparent base material. Furthermore, the substrate is preferably a substrate having a total light transmittance of 80% or more based on JIS K7361-1 (1997), more preferably a substrate having transparency of 90% or more. .

The base material in the conductive laminate of the present invention is preferably resin or glass. As the type of the substrate, an optimum one can be selected from transparency, durability, flexibility, cost, etc. according to the application.

When the substrate is glass, ordinary soda glass can be used. Examples of the resin include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyamide, polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, polycarbonate, polymethyl methacrylate, alicyclic acrylic resin, and cycloolefin resin. , Triacetyl cellulose, and those obtained by mixing and / or copolymerizing these resins, and polyethylene terephthalate is particularly preferable.

The substrate can be a film or a substrate. The resin can be formed into a film by uniaxial stretching or biaxial stretching. The substrate is preferably a film having a thickness of 250 μm or less, particularly preferably a film having a thickness of 190 μm or less, and more preferably a film having a thickness of 150 nm or less, from the viewpoints of cost, productivity, handleability, and the like.

The base material may be a single-layer base material or a composite base material such as a laminate of a plurality of base materials. For example, a base material combining a resin and glass and a base material combining two or more resins can be used.

The base material can be subjected to a surface treatment as necessary. The surface treatment is, for example, physical treatment such as glow discharge, corona discharge, plasma treatment, or flame treatment, or a resin layer may be provided. When the substrate is a film, a film having an easy-adhesion layer may be used.

The conductive laminate of the present invention comprises a base resin layer laminated on at least one surface of a substrate, and the base resin contains a urethane acrylate resin having a glycol skeleton and a resin having a graft structure having a hydrophilic group in the side chain. Resin. When the base resin layer is not provided, even if the conductive laminate is incorporated in the touch panel, writing quality and input sensitivity are not improved and durability is inferior.

The base resin layer of the conductive laminate of the present invention contains a urethane acrylate resin having a glycol skeleton. The urethane acrylate resin is a resin having a urethane structure formed by a reaction between a polyol and a polyfunctional isocyanate, and an end of the reaction product structure is an acrylate. Urethane acrylate resins include, for example, polyols having two or more hydroxyl groups in the molecular structure such as diols, and aliphatic / aromatic / alicyclic polymers having two or more isocyanate groups in the molecular structure such as diisocyanate. After the reaction with the functional isocyanate, the terminal of the reaction product structure is then reacted with an acrylate having a hydroxyl group in the molecular structure (hydroxy functional acrylate) to end-capping to produce a method.

The urethane acrylate resin contained in the base resin layer according to the present invention has a glycol skeleton. When the urethane acrylate resin does not have a glycol skeleton, when used as a touch panel, the writing quality and input sensitivity of the touch panel are not improved and the durability is inferior.

Examples of the glycol skeleton include an ethylene glycol skeleton, a propylene glycol skeleton, a diethylene glycol skeleton, a butanediol skeleton, a hexanediol skeleton, a 1,4-cyclohexanedimethanol skeleton, a glycolic acid skeleton, and a polyglycolic acid skeleton.

The glycol skeleton is more preferably a polyethylene glycol skeleton and / or a polypropylene glycol skeleton. Polyethylene glycol is ethylene glycol, and polypropylene glycol is propylene glycol, which is a polymerized high molecular weight compound that has a longer linear structure and is therefore more flexible when incorporated into the skeleton of urethane acrylate resin. It becomes resin, and it becomes easy to improve the writing quality and input sensitivity of the touch panel.

As the urethane acrylate having a glycol skeleton, for example, a product number selected from Art Resin UN series (manufactured by Negami Kogyo Co., Ltd.) can be used.

The urethane acrylate resin having a glycol skeleton may be contained alone or in combination of two or more in the base resin layer, and these glycol skeletons may be reacted in advance before being incorporated into the urethane acrylate resin skeleton. The base resin layer may contain a urethane acrylate resin having two or more glycol skeletons in the same structure.

In the present invention, preferably, a urethane acrylate resin having a polyethylene glycol skeleton and / or a polypropylene glycol skeleton is contained alone or mixed and contained in the base resin layer. Preferably, the urethane acrylate resin having both the polyethylene glycol skeleton and the polypropylene glycol skeleton in the same structure is obtained by copolymerizing the polyethylene glycol skeleton and the polypropylene glycol skeleton in advance and then incorporating them into the skeleton of the urethane acrylate resin. In the base resin layer. When the urethane acrylate resin having a polyethylene glycol skeleton or a polypropylene glycol skeleton is used as a touch panel, the effect of further improving the writing quality and input sensitivity of the touch panel can be obtained.

When a urethane acrylate resin having a glycol skeleton is contained in the base resin layer, the writing quality and input sensitivity of the touch panel are improved and the durability is good.

The urethane acrylate resin has both a polyol moiety that is a flexible skeleton and an acrylate moiety that is a hard skeleton in its structure. In particular, the glycol skeleton
(1) The linearity of the molecular structure is strong.
(2) Since the oxygen element in the molecular structure is not bonded to an element other than the carbon element (for example, a hydrogen element) and is not subject to spatial inhibition due to steric hindrance of the element other than the carbon element, A large free space,
From these two points, it is presumed that a more flexible urethane acrylate resin can be obtained by introducing it into the polyol moiety. Therefore, it is considered that by including the urethane acrylate resin having the glycol skeleton in the base resin layer, the base resin layer is easily deformed by a load when input with a pen or a finger. On the other hand, since the acrylate part is hard, it is considered that when the load is released, it repels deformation and quickly returns to its original state. As a result, it is estimated that the writing quality is improved because the base resin layer plays a role of a cushion against the load at the time of input, but the present invention is not limited to this estimation.

In the urethane acrylate resin, the number of functional groups at the acrylate moiety in one molecule of urethane acrylate is preferably bifunctional. Since the acrylate portion easily imparts a hard property, the urethane acrylate resin tends to be hard if it exists in a polyfunctionality of 3 or more in one molecule of urethane acrylate, and the cushioning effect of the base resin layer may be reduced. In order to improve the writing quality and input sensitivity, it may be necessary to make adjustments such as increasing the thickness of the base resin layer.

On the other hand, when the number of functional groups in the acrylate moiety is bifunctional, the ratio of the acrylate moiety, that is, the hard part in one molecule of urethane acrylate is small, so that the obtained urethane acrylate resin becomes more flexible and the cushioning effect of the base resin layer is further increased. . For this reason, it becomes easy to further improve the writing quality and input sensitivity of the touch panel.

The number of functional groups in the acrylate moiety can be adjusted by the number of isocyanate functional groups of the aliphatic, aromatic, and alicyclic polyfunctional isocyanates used in the step of synthesizing the urethane acrylate resin. Moreover, as a kind of acrylate site | part, an acrylate, a methacrylate, etc. are mentioned, for example.

As the bifunctional urethane acrylate, specifically, for example, a product number selected from Art Resin UN series (manufactured by Negami Kogyo Co., Ltd.) can be used.

The urethane acrylate resin used in the present invention preferably has an acrylate moiety bonded to another acrylate moiety by polymerization. When the acrylate moiety is bonded to another acrylate moiety, the durability is further improved. As a method for bonding the acrylate moiety, for example, a known photopolymerization initiator is contained together with the urethane acrylate resin in the base resin layer, and the reaction is performed by irradiating with an active electron beam such as ultraviolet light, visible light, or electron beam. There is a way to make it. The photopolymerization initiator is a substance that absorbs light in the ultraviolet region, light in the visible region, electron beam, etc., generates active species such as radical species, cation species, and anion species, and initiates polymerization of the resin. Specifically, for example, a product number selected from Ciba (registered trademark) IRGACURE (registered trademark) series (manufactured by Ciba Japan Co., Ltd.) can be used as the photopolymerization initiator. A photoinitiator may be used individually by 1 type, and may mix 2 or more types.

In the present invention, when the urethane acrylate resin contained in the base resin layer is one kind, the acrylate sites may be bonded to each other in the acrylate sites. When two or more types of urethane acrylate resins contained in the base resin layer are contained, the same type of urethane acrylate resins or different types of urethane acrylate resins may be bonded. Furthermore, when the base resin layer contains a component having an acrylate moiety other than the urethane acrylate resin, it may be combined with a component having an acrylate moiety other than the urethane acrylate resin.

The content of the urethane acrylate resin in the base resin layer is 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, particularly preferably 50% by mass or more, based on the entire base resin layer. Preferably 80 mass% or more is preferable.

The base resin of the conductive laminate of the present invention contains a graft resin having a hydrophilic group in the side chain.

In the present invention, the graft resin is a block polymerization resin, and its structure is illustrated in FIG. FIG. 2 shows a state in which the branched side chains of the backbone polymer as the main chain are bonded in a branch shape. Graft resins come in a variety of forms depending on the type of backbone polymer and side chain, degree of polymerization, molecular weight, molecular chain terminal, molecular chain / branched chain functional group, and degree of crosslinking. It has various performances depending on the degree and molecular weight. The graft resin used in the present invention is a graft resin having a hydrophilic group in the side chain. A graft resin having a hydrophilic group in the side chain has a branched side chain, and even when the trunk polymer is present inside the underlayer, the hydrophilic group reaches the surface of the underlayer, It is possible to impart wettability to the formation.

In the present invention, if the base resin layer contains a resin having a graft structure having a hydrophilic group in the side chain, the surface of the base resin layer is modified and applied uniformly without repelling the dispersion solution of the conductive component. Therefore, it is possible to improve the writing quality and input sensitivity and to supply a conductive laminate having a good appearance and quality with high productivity. On the other hand, when a resin having a graft structure having a hydrophilic group in the side chain is not contained, writing quality and input sensitivity cannot be improved due to defective portions such as unevenness and defects after lamination of the conductive layer.

In the graft resin used in the present invention, the hydrophilic group includes, for example, a hydroxyl group (—OH), a carboxyl group (—COOH), a sulfonic acid group (—SO ₃ H), a phosphoric acid group (H ₂ PO ₄ —), And an amino group (—NH ₂ ). The graft resin may be in a state in which a part of H ⁺ of the hydrophilic group has a counter cation such as Na ⁺ or K ⁺ (for example, —ONa, —COONa, —SO ₃ Na, etc.). The groups may be present alone or in combination of two or more in the branched branch side chain. As the graft resin, a copolymer and / or a mixture of two kinds of graft resins having different hydrophilic groups may be used.

Specific examples of these graft resins having a hydrophilic group in the side chain include L-20, L-40M, LH-448, etc. of Chemitry (registered trademark) series (manufactured by Soken Chemical Co., Ltd.). can do.

The backbone polymer of the graft resin used in the present invention includes, for example, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate resin, polyurethane resin, acrylic resin, methacrylic resin, epoxy resin, polyamide resin, polyimide resin, polyethylene resin, polypropylene Examples thereof include resins such as resin, polystyrene resin, polyvinyl acetate resin, nylon resin, melamine resin, phenol resin, and fluororesin. The graft resin may be used alone, or two or more types of copolymers and / or mixtures may be used. Depending on the application, the graft resin may have a partially crosslinked structure.

It is preferable that a functional group is present in the trunk polymer of the graft resin. More preferably, there is a reactive functional group that forms a bond with each resin or component in the base resin layer, or a functional group that is compatible with an organic solvent or water.

The functional groups of the graft resin trunk polymer include, for example, linear alkyl groups, branched alkyl groups, cycloalkyl groups, alkenyl groups such as vinyl, allyl, hexenyl, and aryls such as phenyl, tolyl, xylyl, styryl, naphthyl, and biphenyl. Groups, aralkyl groups such as benzyl and phenethyl, other aromatic groups including heterocyclic rings such as lactone, oxazole, and imidazole, and ring-opening groups thereof, alkoxy groups such as methoxy, ethoxy, and isopropoxy, acetoxy groups, acrylic groups, and methacrylic groups , Acryloxy groups, methacryloxy groups, oxycarbonyl groups such as allyloxycarbonyl / benzyloxycarbonyl, epoxy groups, isocyanate groups, hydroxyl groups, carboxyl groups, sulfo groups, phosphate groups, amino groups, mercapto sulfides, etc. Elemental sulfur functional groups, nitrogen-containing elements functional groups such as ureido-ketimino, such as halogen-containing elements functional group such as a fluoroalkyl group. Among these functional groups, hydrophilic groups such as hydroxyl group, carboxyl group, sulfonic acid group, phosphoric acid group and amino group can be preferably used. The functional group of the backbone polymer of the graft resin may be used by arbitrarily selecting at least one type depending on the application and required properties, and two or more types may be mixed, and is not particularly limited thereto.

The graft resin in the base resin layer may be contained in any manner in the base resin layer. It may be contained simply in a mixed state, or may exist in a bond with the urethane acrylate resin and other components in the base resin layer.

The content of the graft resin is preferably 5% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 80% by mass or less with respect to the entire base resin layer. If the amount is less than 5% by mass, the modification effect on the surface of the underlying resin layer may be small. If the amount is more than 90% by mass, the writing quality and input sensitivity of the touch panel may be improved depending on the type, structure, and bonding mode of the urethane acrylate resin. The effect may be reduced.

In the conductive laminate of the present invention, the thickness T of the base material and the thickness t of the base resin layer preferably satisfy the following formula.

0.040 ≦ t / T ≦ 0.080
When the conductive laminate satisfying the above formula with the thickness T of the base material and the thickness t of the base resin layer is incorporated into the touch panel, the base resin layer is more likely to be deformed more efficiently with a load when input with a pen or a finger. The writing quality and input sensitivity of the touch panel can be further improved. The value of t / T is more preferably 0.050 or more and 0.070 or less.

In the conductive laminate of the present invention, the base resin layer and the conductive layer are stacked in the order of the base resin layer and the conductive layer from the base material side. In the case where a conductive layer is not provided, conductivity is not exhibited.

In the present invention, the component of the conductive layer is preferably a linear structure. The linear structure in the present invention is a structure in which the ratio of the length of the short axis to the length of the long axis, that is, the aspect ratio = the length of the long axis / the length of the short axis is greater than 1 (on the other hand, For example, a spherical shape has an aspect ratio = 1). Examples of the linear structure include a fibrous conductor and a needle-like conductor such as a whisker. The length of the minor axis is preferably 1 nm to 1000 nm (1 μm). The length of the major axis is preferably such that the aspect ratio = the length of the major axis / the length of the minor axis is greater than 1 with respect to the length of the minor axis. It is preferable that the length of the long axis is 1 μm to 100 μm (0.1 mm) because both optical characteristics and conductive characteristics can be achieved.

The linear structures can be used alone or in combination, and further, other micro-to-nano conductive materials can be added as necessary.

Examples of the fibrous conductor include a carbon-based fibrous conductor, a metal-based fibrous conductor, and a metal oxide-based fibrous conductor. Examples of carbon-based fibrous conductors include polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, rayon-based carbon fibers, glassy carbon, carbon nanotubes, carbon nanocoils, carbon nanowires, carbon nanofibers, carbon whiskers, and graphite fibrils. Etc. Metallic fibrous conductors include gold, platinum, silver, nickel, silicon, stainless steel, copper, brass, aluminum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, manganese, technetium, rhenium, iron, Examples thereof include fibrous or nanowire-like metals and alloys produced from osmium, cobalt, zinc, scandium, boron, gallium, indium, silicon, germanium, tin, magnesium, and the like. Examples of the metal oxide fibrous conductor include InO ₂ , InO ₂ Sn, SnO ₂ , ZnO, SnO ₂ —Sb ₂ O ₄ , SnO ₂ —V ₂ O ₅ , TiO ₂ (Sn / Sb) O ₂ , SiO _{2 2} (Sn / Sb) O ₂ , K ₂ O—nTiO ₂ — (Sn / Sb) O ₂ , K ₂ O—nTiO ₂ —C, etc. manufactured from fibrous or nanowire metal oxides and metal oxides Compound complex and the like. The fibrous conductor may be subjected to a surface treatment.

In addition, as a fibrous conductor, the surface of a non-metallic material such as plant fiber, synthetic fiber, inorganic fiber, gold, platinum, silver, nickel, silicon, stainless steel, copper, brass, aluminum, zirconium, hafnium, vanadium , niobium, tantalum, chromium, molybdenum, manganese, technetium, rhenium, iron, osmium, cobalt, zinc, scandium, boron, gallium, indium, silicon, germanium, tin, _{magnesium, InO 2, InO 2 Sn,} SnO 2, ZnO SnO ₂ —Sb ₂ O ₄ , SnO ₂ —V ₂ O ₅ , TiO ₂ (Sn / Sb) O ₂ , SiO ₂ (Sn / Sb) O ₂ , K ₂ O—nTiO ₂ — (Sn / Sb) O _{2, K 2 O-nTiO 2} -C or carbon nanotubes, also coated or deposited And the like.

In the conductive laminate of the present invention, carbon nanotubes can be preferably used as the fibrous conductor from the viewpoints of optical properties such as transparency and conductivity.

The carbon nanotube will be described. In the present invention, the carbon nanotubes used as components of the conductive layer may be any of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes having three or more layers. Those having a diameter of about 0.3 to 100 nm and a length of about 0.1 to 20 μm are preferably used. In order to increase the transparency of the conductive laminate and reduce the surface resistance, single-walled carbon nanotubes and double-walled carbon nanotubes having a diameter of 10 nm or less and a length of 1 to 10 μm are more preferable.

The aggregate of carbon nanotubes preferably contains as little impurities as possible such as amorphous carbon and catalytic metal. When impurities are contained in the carbon nanotube, it can be appropriately purified by acid treatment or heat treatment.

Carbon nanotubes are synthesized and manufactured by an arc discharge method, a laser ablation method, a catalytic chemical vapor phase method (a method using a catalyst having a transition metal supported on a carrier in a chemical vapor phase method), or the like. It is preferable to produce carbon nanotubes by a catalytic chemical vapor phase method that can reduce the generation of impurities such as amorphous carbon with high productivity.

In the present invention, a conductive layer can be formed by applying a carbon nanotube dispersion. In order to obtain a carbon nanotube dispersion, it is common to perform a dispersion treatment with a carbon nanotube together with a solvent using a mixing and dispersing machine or an ultrasonic irradiation device, and it is desirable to add a dispersant.

The dispersant is a synthetic polymer, natural high polymer in terms of adhesion to the substrate of the conductive layer containing carbon nanotubes coated and dried on the substrate, hardness of the film, and scratch resistance. It is preferred to select a polymer of molecules. Furthermore, a crosslinking agent may be added within a range that does not impair the dispersibility.

Synthetic polymers include, for example, polyether diol, polyester diol, polycarbonate diol, polyvinyl alcohol, partially saponified polyvinyl alcohol, acetoacetyl group-modified polyvinyl alcohol, acetal group-modified polyvinyl alcohol, butyral group-modified polyvinyl alcohol, silanol group-modified polyvinyl alcohol, Ethylene-vinyl alcohol copolymer, ethylene-vinyl alcohol-vinyl acetate copolymer resin, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, acrylic resin, epoxy resin, modified epoxy resin, phenoxy resin, modified phenoxy resin, phenoxy Ether resin, phenoxy ester resin, fluorine resin, melamine resin, alkyd resin, phenol resin, polyacrylic resin Amides, polyacrylic acid, polystyrene sulfonic acid, polyethylene glycol, polyvinylpyrrolidone. Natural polymers include, for example, polysaccharides such as starch, pullulan, dextran, dextrin, guar gum, xanthan gum, amylose, amylopectin, alginic acid, gum arabic, carrageenan, chondroitin sulfate, hyaluronic acid, curdlan, chitin, chitosan, cellulose and the like It can be selected from derivatives. The derivative means a conventionally known compound such as ester or ether. These may be used alone or in combination of two or more. Among these, polysaccharides and derivatives thereof are preferable because of excellent dispersibility of the carbon nanotubes. Furthermore, cellulose and derivatives thereof are preferable because of high film forming ability. Of these, esters and ether derivatives are preferable, and specifically, carboxymethyl cellulose and salts thereof are preferable.

It is also possible to adjust the compounding ratio of the carbon nanotube and the dispersant. The compounding ratio of the carbon nanotubes and the dispersant is preferably a compounding ratio that does not cause problems in adhesion to the substrate, hardness, and scratch resistance. Specifically, the carbon nanotubes are preferably in the range of 10% by mass to 90% by mass with respect to the entire conductive layer. More preferably, it is in the range of 30% to 70% by mass. When the carbon nanotubes are 10% by mass or more, the conductivity required for the touch panel is easily obtained, and furthermore, it is easy to apply uniformly without being repelled when applied to the surface of the base material. The conductive laminate having the above can be supplied with high productivity. When the carbon nanotubes are 90% by mass or less, the dispersibility of the carbon nanotubes in the solvent is improved and it is difficult to agglomerate, a good carbon nanotube coating layer is easily obtained, and the productivity is good. Furthermore, the coating film is also strong, and it is preferable because scratches are less likely to occur during the production process and the uniformity of the surface resistance value can be maintained.

The acicular conductor is preferably an acicular conductor that is a compound made of a metal, a carbon-based compound, a metal oxide, or the like. The metal belongs to the group IIA, IIIA, IVA, VA, VIA, VIIA, VIII, IB, IIB, IIIB, IVB or VB in the short periodic table of elements. Elements. Specifically, gold, platinum, silver, nickel, stainless steel, copper, brass, aluminum, gallium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, manganese, antimony, palladium, bismuth, technetium, rhenium, Examples thereof include iron, osmium, cobalt, zinc, scandium, boron, gallium, indium, silicon, germanium, tellurium, tin, magnesium, and alloys containing these. Examples of the carbon-based compound include carbon nanohorn, fullerene, and graphene. Examples of the metal oxide include InO ₂ , InO ₂ Sn, SnO ₂ , ZnO, SnO ₂ —Sb ₂ O ₄ , SnO ₂ —V ₂ O ₅ , TiO ₂ (Sn / Sb) O ₂ , SiO ₂ (Sn / Sb ) O ₂ , K ₂ O—nTiO ₂ — (Sn / Sb) O ₂ , K ₂ O—nTiO ₂ —C, and the like.

In the conductive laminate of the present invention, silver nanowires can be preferably used as the acicular conductor from the viewpoints of optical properties such as transparency and conductivity.

Examples of the acicular conductor include WK200B, WK300R, and WK500 of DENTOR WK series (manufactured by Otsuka Chemical Co., Ltd.), which is a composite compound of potassium titanate fiber, tin, and antimony oxide, and silicon dioxide fiber and tin. DENTOR TM series (manufactured by Otsuka Chemical Co., Ltd.) TM100, which is a complex compound of antimony oxide, is commercially available.

In the conductive laminate of the present invention, the surface resistance value on the conductive layer side is preferably 1 × 10 ⁰ Ω / □ or more and 1 × 10 ⁴ Ω / □ or less, more preferably 1 × 10 ¹ Ω / □. The above is 1.5 × 10 ³ or less. When the surface resistance value is 1 × 10 ⁰ Ω / □ or more and 1 × 10 ⁴ Ω / □ or less, it can be preferably used as a conductive laminate for a touch panel. That is, if it is 1 × 10 ⁰ Ω / □ or more, power consumption can be reduced, and if it is 1 × 10 ⁴ Ω / □ or less, the influence of errors in the coordinate reading of the touch panel can be reduced.

As the underlying resin layer is deformed, the conductive layer laminated thereon is also deformed. It is estimated that the area of the contact surface that contributes to the conduction increases due to the deformation of the conductive layer, and as a result, the input current is improved because the total amount of flowing current increases even with a small input load. It is not limited to this estimation.

The conductive laminate of the present invention is preferably a transparent conductive laminate having a total light transmittance of 80% or more based on JIS K7361-1 (1997) when incident from the conductive layer side. When the conductive laminate of the present invention is incorporated into a touch panel as a transparent conductive laminate, the touch panel not only has good writing quality and input sensitivity, but also exhibits excellent transparency, and the lower layer of the touch panel using this transparent conductive laminate. The display on the display can be clearly recognized. The transparency in the present invention means that the total light transmittance based on JIS K7361-1 (1997) when incident from the conductive layer side is 80% or more, preferably 85% or more, more Preferably it is 90% or more. Examples of the method for increasing the total light transmittance include, for example, a method for increasing the total light transmittance of a substrate to be used, a method for reducing the thickness of the conductive layer, and a conductive layer provided on the base resin layer. And a method of laminating a transparent protective layer to be an optical interference film. As a method of increasing the total light transmittance of the base material, a method of reducing the thickness of the base material or a method of selecting a base material made of a material having a large total light transmittance can be mentioned.

In the conductive laminate of the present invention, a base resin layer containing a urethane acrylate resin having a glycol skeleton and a resin having a graft structure having a hydrophilic group in a side chain is formed on a base resin layer. It can be preferably manufactured in the step of forming the conductive layer. More preferably, in the conductive laminate of the present invention, the conductive layer is formed by applying a water-containing dispersion of carbon nanotubes or silver nanoware and then drying.

Various additives can be added to the base material and / or each layer according to the present invention within a range that does not impair the effects of the present invention. Examples of the additives include organic and / or inorganic fine particles, crosslinking agents, flame retardants, flame retardant aids, heat stabilizers, oxidation stabilizers, leveling agents, slip activators, conductive agents, antistatic agents, and ultraviolet rays. Absorbers, light stabilizers, nucleating agents, dyes, fillers, dispersants, coupling agents, and the like can be used.

In the conductive laminate of the present invention, a protective layer is preferably formed on the conductive layer.

The conductive layer reflects and absorbs light due to the physical properties of the conductive component itself. Therefore, in order to increase the total light transmittance of the transparent conductive laminate including the conductive layer provided on the substrate, a transparent protective layer serving as an optical interference film with a transparent material is provided on the conductive layer. It is preferable to reduce the average reflectance at a wavelength of 380 to 780 nm to 4% or less. The average reflectance at a wavelength of 380 to 780 nm on the optical interference film side is preferably 3% or less, more preferably 2% or less. When the average reflectance is 4% or less, a performance with a total light transmittance of 80% or more when used for touch panel applications can be obtained with good productivity. In addition, the presence of the transparent protective layer is preferable because generation of interference fringes due to interference of reflected light between the upper and lower sides through the space 5 on the touch panel shown in FIG. 4 can be suppressed.

In the conductive laminate of the present invention, as a transparent protective layer serving as an optical interference film provided on the conductive layer, in addition to the role of this optical interference, it also has the role of improving the scratch resistance of the conductive layer and preventing the conductive component from falling off. It is more preferable to use a transparent protective film.

In order to reduce the average reflectance, the transparent protective layer preferably has a refractive index of the transparent protective layer lower than that of the conductive layer and a difference from the refractive index of the conductive layer of 0.3 or more, more preferably 0. It is preferable to use 4 or more. If the refractive index of the transparent protective layer is 0.3 or more, the control range in which the average reflectance is 4% or less is widened, and the process margin in production is increased, which is preferable.

The transparent protective layer is preferably composed of an inorganic compound, an organic compound, and an inorganic / organic composite and having a structure having a cavity inside. Single substances include inorganic compounds such as silicon oxide, magnesium fluoride, cerium fluoride, lanthanum fluoride, and calcium fluoride, organic compounds such as polymers containing silicon element and fluorine element, Obtained by polymerizing fine particles of silica, acryl, etc. having voids and monofunctional or polyfunctional (meth) acrylic acid ester, or / and siloxane compounds, and / or organic compounds having perfluoroalkyl groups. There are mixtures with polymers to be prepared.

Specific examples of the silicon oxide include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, and methyltrimethoxysilane. , Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane N-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane Vinyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltri Ethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydride Xylpropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyl Triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Triethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-urei Examples include trialkoxysilanes such as dopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, vinyltriacetoxysilane, and organoalkoxysilanes such as methyltriacetyloxysilane and methyltriphenoxysilane. In addition, a coating layer such as a sol-gel coating layer that forms a coating solution obtained by hydrolyzing these silicon oxides with various solvents such as alcohol, water, and acid by a polymerization reaction may be used. A vapor-deposited layer or a sputtered layer can be used.

Further, as a composite using silica fine particles having cavities inside, Opstar (registered trademark) TU-2180 (manufactured by JSR Co., Ltd.) or the like can be specifically used.

As a method for forming the base resin layer, the conductive layer, and the transparent protective layer on the conductive layer in the present invention, an optimal method may be selected depending on the material to be formed, and a dry method such as vacuum deposition, EB deposition, or sputtering. General methods such as casting, spin coating, dip coating, bar coating, spraying, blade coating, slit die coating, gravure coating, reverse coating, screen printing, mold coating, printing transfer, inkjet, etc. Can do. Among them, the base resin layer, the conductive layer, and the transparent protective layer can be uniformly laminated, and the slit die coat that prevents the conductive layer from being scratched, or the base resin layer, the conductive layer, and the transparent protective layer can be formed uniformly and with high productivity. A wet coating method using microgravure is preferred. The conductive laminate of the present invention is preferably produced by a production method including a step of forming a transparent protective layer, which is a more preferable embodiment, on the conductive layer.

Next, the touch panel of the present invention will be described. FIG. 4 is a schematic cross-sectional view showing an example of a resistive film type touch panel. The resistive touch panel has a configuration in which an upper electrode 13 is fixed on a lower electrode 14 by a frame-like double-sided adhesive tape 19. The base resin layer 2 and the conductive layer 3 are laminated in this order on the base materials 15 and 16 constituting the upper and lower electrodes, and the conductive layers 3 of the upper and lower electrodes sandwich the space 20. Oppositely formed in a planar shape. Further, the transparent protective layer 4 may be provided on the conductive layer 3 of the substrate 15 or 16. Dot spacers 18 are provided in the space 20 at regular intervals, thereby holding a gap between the upper and lower conductive layers. The upper surface of the base material 15 is a surface where the pen 22 and the tip of the finger come into contact, and a hard coat layer 17 is provided to prevent scratches. In this touch panel, voltage is applied by the power source 21 and the surface of the hard coat layer 17 is pushed by the pen 22 or the tip of a finger to apply a load, whereby electricity flows from the contacted portion. The touch panel having the above configuration is used, for example, by attaching a lead wire and a drive unit and incorporating it on the front surface of the liquid crystal display.

Since the resistive film type touch panel shown in FIG. 4 is configured through the space 20, the base resin layer is deformed by a load when input with a pen or a finger, thereby improving the writing quality and input sensitivity of the touch panel. This is a touch panel configuration that is extremely effective and has the highest effect of using the conductive laminate of the present invention.

Hereinafter, the present invention will be specifically described based on examples. An evaluation method in each example and comparative example will be described.

(1) Identification of structure and bonding mode of compound in each layer First, a sample is immersed in a solvent, each layer is peeled and collected, and the solvent after immersion is filtered. When there was a filter cake, a solvent having high solubility in the filter cake was selected and dissolved again. Next, a separable method is selected from general chromatography represented by silica gel column chromatography, gel permeation chromatography, liquid high-performance chromatography, gas chromatography, etc., and the filtrate and the redissolved filtrate solution are each simply used. Separated and purified to one substance. When separation with other components was difficult, it was used as it was.

Thereafter, each substance is appropriately concentrated and diluted, and nuclear magnetic resonance spectroscopy ( ¹ H-NMR, ¹³ C-NMR), two-dimensional nuclear magnetic resonance spectroscopy (2D-NMR), infrared spectrophotometry (IR), Raman spectroscopy, mass spectrometry (Mass), X-ray diffraction (XRD), neutron diffraction (ND), low-energy electron diffraction (LEED), high-energy reflection electron diffraction (RHEED), atomic absorption spectrometry ( AAS), ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS), X-ray fluorescence elemental analysis (XRF), inductively coupled plasma emission spectroscopy (ICP-AES), electron beam microanalyzer (EPMA), Structural identification was performed by appropriately selecting and combining methods from gel permeation chromatography (GPC) and other elemental analysis.

(2) Surface resistance value R ₀
The surface resistance on the conductive layer side was measured at a central portion of a 100 mm × 50 mm sample by a four-probe method using a low resistivity meter Loresta-EP MCP-T360 (manufactured by Mitsubishi Chemical Corporation). An average value was calculated for five samples, and this was defined as a surface resistance value _R0 .

(3) Durability The sample of (2) above was heated in a thermostatic safety oven with a safety door (SPHH-201, manufactured by Espec Corp.) at 150 ° C. for 1 hour, and then the same method as in (2) above Then, the surface resistance value R at the same position was measured again to calculate R / R ₀ (R ₀ is a value obtained by the above item (2)). Similarly, it implemented about 5 samples and made the average value of each R / _R0 the durability index as the rate of increase of the surface resistance value. The determination criteria in the present invention were determined as follows.
Class A: R / R ₀ ≦ 1.5
Class B: 1.5 <R / R ₀ ≦ 1.8
Class C: R / R ₀ > 1.8
If it is A and B class, it will be a pass and A class is the most preferable.

(4) Base material thickness T, base resin layer thickness t
The sample was cut in a direction perpendicular to the sample plane at a knife inclination angle of 3 ° using a rotary microtome manufactured by Nippon Microtome Laboratories. Using the scanning electron microscope ABT-32 manufactured by Topcon Corporation, select any three magnifications from an observation magnification of 2500 to 10000 times, and adjust the contrast of the image as appropriate, and observe the obtained sample cross section at each magnification. From the obtained cross-sectional photograph, arbitrary five locations respectively corresponding to the base material and the base resin layer were similarly measured at arbitrary three magnifications (calculated from the enlargement magnification), and the average values of the total 15 locations were thicknesses T and t, respectively. It was.

(5) Structure of conductive component The surface of the sample on the conductive layer side is accelerated at an acceleration voltage of 3.0 kV by using a field emission scanning electron microscope (JSM-6700-F manufactured by JEOL Ltd.) or atomic force. The images were observed with a microscope (NanoScope III manufactured by Digital Instruments). In the case where the surface could not be observed by surface observation, the components of the conductive layer were separated and purified by any of the methods similar to (1), and then the substances corresponding to the conductive components were collected and collected, and then observed in the same manner.

(6) Total light transmittance Total light transmittance in the thickness direction of the conductive laminate based on JIS K7361-1 (1997) using a turbidimeter (cloudiness meter) NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.) The rate was measured by making light incident from the conductive layer side. The average value of the values measured for the five samples was calculated and used as the total light transmittance.

(7) Touch quality and input sensitivity of touch panel In the present invention, the indicators of the text quality and input sensitivity are the ON load [g] and the contact resistance value [kΩ]. The ON load is, for example, the minimum load at which the touch panel can be operated for the first time when the touch panel shown in FIG. 4 is loaded with the pen 22, and the touch panel can operate. The ON load is weaker. This means that the touch panel can be operated with force, and is an indicator of writing quality. Further, the contact resistance is a resistance value when electricity flows from the surface where the upper and lower electrodes in FIG. 4 are in contact with each other when a load is applied, and the upper and lower electrodes are in contact via the space 20. If not, the insulation state is established, the contact resistance value becomes infinite, and electricity does not flow. The lower the contact resistance value, the better the input sensitivity is.

The ON load and contact resistance value were determined as follows. First, in the touch panel of FIG. 4, conductive glass with ITO (made by Touch Panel Laboratories Co., Ltd.) is used as the lower electrode 14, and the conductive laminates of the examples and comparative examples of the present invention are used as the upper electrode, respectively. A touch panel was prepared. Next, using a HEIDON TRIBOGEAR surface property measuring instrument TYPE: HEIDON-14DR (manufactured by Shinto Kagaku Co., Ltd.), a polyacetal pen with a radius of 0.8 mm on the sample stage side of the attached load unit. 8R (manufactured by Touch Panel Laboratories Co., Ltd.) was set, and the prepared touch panel was placed on the sample stage so that the pen tip was at the center position of the touch panel (vertical position 35 mm, horizontal position 50 mm). Load the weights on the load unit in increments of 1 g up to 300 g and apply the load with the pen, and read the value of the contact resistance for each load. Moreover, the weight of the weight which showed the value of contact resistance for the first time was made into ON load. Similarly, 3 times per sample and 3 times of 3 samples were carried out, and the average value was defined as the contact resistance value and ON load of the present invention.

(8) Appearance of the conductive laminate The conductive layer side of the conductive laminate was visually observed under a fluorescent lamp from 90 ° direction (vertical direction), 45 ° direction, and 10 ° direction with respect to the conductive surface. The determination criteria in the present invention were determined as follows by judging whether or not the conductive layer defects (such as repelling) were visually recognized.
Class A: No defects in all angle directions Class B: Defects in any angle direction C class: Defects in all angle directions: A and B are acceptable, and Class A is most preferred.

(9) Refractive index For coating films formed on a silicon wafer or quartz glass with a coater, using a high-speed spectrophotometer M-2000 (manufactured by JA Woollam), changes in the polarization state of the reflected light of the coating film Was measured at an incident angle of 60 degrees, 65 degrees, and 70 degrees, and the refractive index at a wavelength of 550 nm was obtained by calculation using analysis software WVASE32.

(10) Film thickness of transparent protective layer The film thickness of the transparent protective film of the produced transparent conductive laminate was measured by using an electric field emission scanning electron microscope (JSM-6700-F, manufactured by JEOL Ltd.) with an acceleration voltage of 3. Three arbitrary magnifications were selected from observation magnifications of 10,000 to 200,000 at 0 kV, and images were observed at various magnifications by appropriately adjusting the contrast of the image. The sample cross-section was adjusted using the microtome described in the item (4). From any of the obtained cross-sectional photographs, five arbitrary positions were similarly measured at three arbitrary magnifications (calculated from the magnification), and the values at a total of 15 positions were averaged.

(11) Average reflectance When a transparent protective layer was provided, the average reflectance was determined by the following method.

The surface opposite to the transparent measurement surface (the surface on which the transparent protective layer is provided) is evenly distributed with water resistant sandpaper No. 320-400 so that the 60 ° C glossiness (JIS Z 8741 (1997)) is 10 or less. After roughening, a black paint was applied and colored so that the visible light transmittance was 5% or less. Using a spectrophotometer (UV-3150) manufactured by Shimadzu Corporation, the absolute reflection spectrum in the wavelength region of 300 nm to 800 nm was measured at an interval of 1 nm at an incident angle of 5 degrees from the measurement surface, and at a wavelength of 380 nm to 780 nm. Average reflectance was determined.

Resins, photopolymerization initiators, and films used in Examples and Comparative Examples are shown below.

(1) Resin A
Art Resin LPVC-3 (manufactured by Negami Kogyo Co., Ltd., polypropylene glycol skeleton bifunctional urethane acrylate, solid concentration 100 mass%).

(2) Resin B
Chemitly (registered trademark) L-20 (manufactured by Soken Chemical Co., Ltd., graft acrylic having a hydroxyl group (—OH) as a hydrophilic group in the side chain, solid content concentration: 26 mass% solution).

(3) Resin C
Art Resin UN-7600 (manufactured by Negami Kogyo Co., Ltd., polyester skeleton bifunctional urethane acrylate, solid concentration 100 mass%).

(4) Resin D
Aronix (registered trademark) M240 (manufactured by Toagosei Co., Ltd., polyethylene glycol skeleton bifunctional acrylate, solid concentration 100 mass%).

(5) Resin E
Aronix (registered trademark) M270 (manufactured by Toagosei Co., Ltd., polypropylene glycol skeleton bifunctional acrylate, solid concentration 100 mass%).

(6) Resin F
TRSC-006 (manufactured by Negami Kogyo Co., Ltd., polypropylene glycol skeleton bifunctional urethane, solid concentration 58.8% by mass solution).

(7) Resin G
X-22-8114 (manufactured by Shin-Etsu Chemical Co., Ltd., graft acrylic, which is a silicone having a side chain having a methyl group (—CH ₃ ) and an n-butyl (—CH ₂ CH ₂ CH ₂ CH ₃ ) group, solid content 40% by weight solution).

(8) Photopolymerization initiator Ciba IRGACURE (registered trademark) 184 (manufactured by Ciba Japan Co., Ltd.).

(9) Film Polyethylene terephthalate film, Lumirror (registered trademark) U46 (manufactured by Toray Industries, Inc.).

The conductive layers in Examples and Comparative Examples are shown below.

(1) Conductive layer A “Carbon nanotube conductive layer”
(Catalyst adjustment)
2.459 g of ammonium iron citrate (green) (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 500 mL of methanol (manufactured by Kanto Chemical Co., Inc.). To this solution, 100 g of light magnesia (Iwatani Chemical Industry Co., Ltd.) was added, stirred at room temperature for 60 minutes, dried under reduced pressure while stirring at 40 ° C. to 60 ° C. to remove methanol, and a metal salt was added to the light magnesia powder. Was obtained.

(Production of carbon nanotube composition)
Carbon nanotubes were synthesized in a fluidized bed vertical reactor shown in the schematic diagram of FIG. The reactor 100 is a cylindrical quartz tube having an inner diameter of 32 mm and a length of 1200 mm. A quartz sintered plate 101 is provided at the center, an inert gas and source gas supply line 104 is provided at the lower part of the quartz tube, and an exhaust gas line 105 and a catalyst charging line 103 are provided at the upper part. In addition, a heater 106 is provided that surrounds the circumference of the reactor so that the reactor can be maintained at an arbitrary temperature. The heater 106 is provided with an inspection port 107 so that the flow state in the apparatus can be confirmed.

12 g of the catalyst was taken, and the catalyst 108 shown in the “catalyst adjustment” portion was set on the quartz sintered plate 101 through the catalyst charging line 103 from the sealed catalyst supplier 102. Subsequently, supply of argon gas from the source gas supply line 104 was started at 1000 mL / min. After the inside of the reactor was placed in an argon gas atmosphere, the temperature was heated to 850 ° C.

After reaching 850 ° C., the temperature was maintained, the argon flow rate of the raw material gas supply line 104 was increased to 2000 mL / min, and fluidization of the solid catalyst on the quartz sintered plate was started. After confirming fluidization from the heating furnace inspection port 107, supply of methane to the reactor at 95 mL / min was started. After supplying the mixed gas for 90 minutes, the flow was switched to a flow of only argon gas, and the synthesis was terminated.

The heating was stopped and the mixture was allowed to stand at room temperature, and after reaching room temperature, the carbon nanotube composition containing the catalyst and carbon nanotubes was taken out from the reactor.

23.4 g of the carbon nanotube composition with catalyst shown above was put on a magnetic dish and heated in a muffle furnace (FP41, manufactured by Yamato Scientific Co., Ltd.) that had been heated to 446 ° C. for 2 hours at 446 ° C. for 2 hours. After heating, it was removed from the muffle furnace. Next, in order to remove the catalyst, the carbon nanotube composition was added to a 6N aqueous hydrochloric acid solution and stirred at room temperature for 1 hour. The recovered product obtained by filtration was further added to a 6N aqueous hydrochloric acid solution and stirred at room temperature for 1 hour. After filtering this and washing with water several times, 57.1 mg of the carbon nanotube composition from which magnesia and metal have been removed can be obtained by drying the filtrate overnight in an oven at 120 ° C. The above procedure is repeated. Thus, 500 mg of a carbon nanotube composition from which magnesia and metal were removed was prepared.

Next, 80 mg of the carbon nanotube composition from which the catalyst has been removed by heating in a muffle furnace is added to 27 mL of concentrated nitric acid (1st grade Assay 60-61%, manufactured by Wako Pure Chemical Industries, Ltd.), and 5 hours in an oil bath at 130 ° C. Heated with stirring. After heating and stirring, the nitric acid solution containing carbon nanotubes was filtered, washed with distilled water, and 1266.4 mg of carbon nanotube composition was obtained in a wet state containing water.

(Carbon nanotube dispersion coating solution)
In a 50 mL container, 10 mg of the above carbon nanotube composition (converted when dried), 10 mg of sodium carboxymethylcellulose (Sigma, 90 kDa, 50-200 cps) as a dispersant, add distilled water to 10 g, and output an ultrasonic homogenizer of 20 W. Then, the dispersion treatment was carried out under ice cooling for 20 minutes to prepare a carbon nanotube coating solution. The obtained liquid was centrifuged at 10,000 G for 15 minutes with a high-speed centrifuge to obtain 9 mL of the supernatant. 5 mL of ethanol was added to 145 mL of supernatant obtained by repeating this operation several times, and a carbon nanotube dispersion coating liquid (carbon nanotube / dispersing agent mixing ratio of 1: 1) having a carbon nanotube concentration of about 0.1% by mass that can be applied by a coater. Obtained. The carbon nanotube conductive layer coated and dried with this carbon nanotube dispersion coating liquid on quartz glass had a refractive index of 1.82.

(Formation of carbon nanotube conductive layer)
The carbon nanotube dispersion coating liquid was applied with a micro gravure coater (gravure wire number 100R or 150R, gravure rotation ratio 80%) and dried at 100 ° C. for 1 minute to provide a carbon nanotube coating film.

(2) Conductive layer B "Silver nanowire conductive layer"
Silver nanowires were obtained by the method disclosed in Example 1 (synthesis of silver nanowires) of International Publication No. WO2007 / 022226. Next, a silver nanowire-dispersed coating liquid was obtained by the method disclosed in Example 8 (nanowire dispersion) of International Publication No. WO2007 / 022226. This silver nanowire-dispersed coating solution was applied using a bar coater manufactured by Matsuo Sangyo Co., Ltd. and dried at 120 ° C. for 2 minutes to provide a silver nanowire coating film.

(3) Conductive layer C “ITO conductive layer”
Using an indium tin oxide target having a composition of In ₂ O ₂ / SnO ₂ = 90/10, an ITO conductive film having a thickness of 250 nm was formed by sputtering under an argon / oxygen mixed gas introduction at a vacuum degree of 10 ⁻⁴ Torr. A functional thin film was provided.

The transparent protective layer in Examples and Comparative Examples is shown below. The transparent protective layer was laminated on the conductive layer by the methods of Examples and Comparative Examples.

(1) Transparent protective layer material A
In a 100 mL plastic container, 20 g of ethanol was added, and 40 g of n-butyl silicate was added and stirred for 30 minutes. Thereafter, 10 g of 0.1N hydrochloric acid aqueous solution was added, and the mixture was stirred for 2 hours (hydrolysis reaction) and stored at 4 ° C. On the next day, this solution was diluted with an isopropyl alcohol / toluene / n-butanol mixed solution (mixing mass ratio 2/1/1) so that the solid concentration was 1.0, 1.2, and 1.5% by mass. . The refractive index of the transparent protective layer of silicon oxide obtained by applying this solution to a silicon wafer and drying was 1.44.

(2) Transparent protective layer material B
A hollow silica particle-containing acrylic UV curable low refractive index material TU-2180 (solid content concentration 10 mass%) manufactured by JSR Corporation was diluted with methyl ethyl ketone so that the solid content concentration was 1.5 mass%. The refractive index of the silicon oxide transparent protective layer obtained by applying this solution to a silicon wafer and drying was 1.37.

Example 1
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd., solid content concentration 82% by mass) on one side with a “film” having a thickness of 188 μm as a base material and a solid content concentration of 40: 1 with toluene / methyl ethyl ketone mass% ratio. A hard coating agent diluted to mass% is applied with a micro gravure coater (gravure wire number 80R, gravure rotation ratio 100%), dried at 80 ° C. for 1 minute, irradiated with ultraviolet rays at 1.0 J / cm ² and cured to a thickness of 5 μm. The hard coat layer was provided.

Next, 1.40 g of “resin A”, 13.85 g of “resin B”, and 2.00 g of ethyl acetate were mixed and stirred to prepare a base resin layer coating solution. This base resin layer coating solution is applied to the opposite surface of the base material provided with the hard coat layer using a bar coater count 30 manufactured by Matsuo Sangyo Co., Ltd., and dried by heating at 100 ° C. for 3 minutes. A base resin layer having a subsequent coating thickness of 13 μm was provided.

Next, “conductive layer A” was laminated on the base resin layer with a gravure wire number 150R to obtain a conductive laminate of the present invention.

Example 2
The composition of the base resin layer coating solution is 1.40 g of “resin A”, 13.96 g of “resin B”, 0.041 g of “photopolymerization initiator”, and 2.08 g of ethyl acetate. Created in the same manner as in Example 1 except that ultraviolet rays were irradiated at 1.2 J / cm ² , and “conductive layer A” was laminated with gravure wire number 150R on a base resin layer having a coating thickness after drying of 13 μm. The conductive laminate of the present invention was obtained.

Example 3
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd., solid content concentration 82% by mass) on one side with a “film” having a thickness of 188 μm as a base material and a solid content concentration of 40: 1 with toluene / methyl ethyl ketone mass% ratio. A hard coating agent diluted to mass% is applied with a micro gravure coater (gravure wire number 80R, gravure rotation ratio 100%), dried at 80 ° C. for 1 minute, irradiated with ultraviolet rays at 1.0 J / cm ² and cured to a thickness of 5 μm. The hard coat layer was provided.

Next, 3.48 g of “Resin A”, 8.92 g of “Resin B” and 7.59 g of ethyl acetate were mixed and stirred to prepare a base resin layer coating solution. This base resin layer coating solution is applied to the opposite surface of the base material provided with the hard coat layer using a bar coater count 30 manufactured by Matsuo Sangyo Co., Ltd., and dried by heating at 100 ° C. for 3 minutes. A base resin layer having a subsequent coating thickness of 13 μm was provided.

Next, “conductive layer B” was laminated on the base resin layer to obtain a conductive laminate of the present invention.

Example 4
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd., solid concentration 82 mass%) on one side with a “film” having a thickness of 125 μm as a one-to-one ratio of toluene to methyl ethyl ketone mass ratio 40 A hard coating agent diluted to mass% is applied with a micro gravure coater (gravure wire number 80R, gravure rotation ratio 100%), dried at 80 ° C. for 1 minute, irradiated with ultraviolet rays at 1.0 J / cm ² and cured to a thickness of 5 μm. The hard coat layer was provided.

Next, 3.64 g of “resin A”, 1.38 g of “resin B”, and 14.97 g of ethyl acetate were mixed and stirred to prepare a base resin layer coating solution. This base resin layer coating solution is applied to the opposite side of the base material provided with the hard coat layer using a bar coater count 24 manufactured by Matsuo Sangyo Co., Ltd., and dried by heating at 100 ° C. for 3 minutes. A base resin layer having a subsequent coating thickness of 7 μm was provided. Next, “conductive layer B” was laminated on the base resin layer to obtain a conductive laminate of the present invention.

Example 5
The base resin layer coating solution was prepared in the same manner as in Example 4 except that 3.84 g of “resin A”, 0.62 g of “resin B”, and 15.55 g of ethyl acetate, and the coating thickness after drying was A “conductive layer B” was laminated on a 7 μm ground resin layer to obtain a conductive laminate of the present invention.

Example 6
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd., solid concentration 82 mass%) on one side with a “film” having a thickness of 125 μm as a one-to-one ratio of toluene to methyl ethyl ketone mass ratio 40 A hard coating agent diluted to mass% is applied with a micro gravure coater (gravure wire number 80R, gravure rotation ratio 100%), dried at 80 ° C. for 1 minute, irradiated with ultraviolet rays at 1.0 J / cm ² and cured to a thickness of 5 μm. The hard coat layer was provided.

Next, 1.40 g of “resin A”, 13.96 g of “resin B”, 0.041 g of “photopolymerization initiator”, and 9.95 g of ethyl acetate were mixed and stirred to prepare a base resin layer coating solution. This base resin layer coating solution is applied to the opposite surface of the base material provided with the hard coat layer using a bar coater count 24 manufactured by Matsuo Sangyo Co., Ltd. 1.2 J / cm ^{2 was} irradiated and cured, and a base resin layer having a coating thickness of 7 μm was provided.

Next, “conductive layer A” was laminated on the base resin layer with a gravure wire number 150R to obtain a conductive laminate of the present invention.

Example 7
The composition of the base resin layer coating solution is 1.80 g of “resin A”, 8.48 g of “resin B”, 0.043 g of “photopolymerization initiator”, and 9.92 g of ethyl acetate. Except that the ultraviolet ray was irradiated at 1.2 J / cm ² , it was prepared in the same manner as in Example 6, and the “conductive layer A” was laminated on the base resin layer having a coating thickness of 7 μm with a gravure wire number 150R. A conductive laminate was obtained.

Example 8
The composition of the base resin layer coating solution is 1.00 g of “resin A”, 16.40 g of “resin B”, 0.030 g of “photopolymerization initiator”, 9.04 g of ethyl acetate, and after applying and drying the coating solution, Except that the ultraviolet ray was irradiated at 1.2 J / cm ² , it was prepared in the same manner as in Example 6, and the “conductive layer A” was laminated on the base resin layer having a coating thickness of 7 μm with a gravure wire number 150R. A conductive laminate was obtained.

Example 9
The composition of the base resin layer coating solution was 0.80 g of “resin A”, 18.90 g of “resin B”, 0.024 g of “photopolymerization initiator”, and 8.97 g of “ethyl acetate”, and the coating solution was applied and dried. Later, it was prepared in the same manner as in Example 6 except that ultraviolet rays were further irradiated at 1.2 J / cm ² , and “conductive layer A” was laminated with gravure wire number 150R on the base resin layer having a coating thickness of 7 μm. The conductive laminate of the present invention was obtained.

Example 10
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd., solid concentration 82 mass%) on one side with a “film” having a thickness of 125 μm as a one-to-one ratio of toluene to methyl ethyl ketone mass ratio 40 A hard coating agent diluted to mass% is applied with a micro gravure coater (gravure wire number 80R, gravure rotation ratio 100%), dried at 80 ° C. for 1 minute, irradiated with ultraviolet rays at 1.0 J / cm ² and cured to a thickness of 5 μm. The hard coat layer was provided.

Next, 0.50 g of “resin A”, 19.44 g of “resin B”, 0.015 g of “photopolymerization initiator”, and 0.67 g of ethyl acetate were mixed and stirred to prepare a base resin layer coating solution. This base resin layer coating solution was applied to the opposite surface of the base material provided with the hard coat layer using a bar coater count 26 manufactured by Matsuo Sangyo Co., Ltd. Was irradiated and cured to 1.2 J / cm ² to provide a base resin layer having a coating thickness of 10.5 μm.

Next, “conductive layer A” was laminated on the base resin layer with a gravure wire number 150R to obtain a conductive laminate of the present invention.

Example 11
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd., solid concentration 82 mass%) on one side with a “film” having a thickness of 125 μm as a one-to-one ratio of toluene to methyl ethyl ketone mass ratio 40 A hard coating agent diluted to mass% is applied with a micro gravure coater (gravure wire number 80R, gravure rotation ratio 100%), dried at 80 ° C. for 1 minute, irradiated with ultraviolet rays at 1.0 J / cm ² and cured to a thickness of 5 μm. The hard coat layer was provided.

Next, 1.00 g of “resin A”, 9.89 g of “resin B”, 0.030 g of “photopolymerization initiator” and 7.09 g of ethyl acetate were mixed and stirred to prepare a base resin layer coating solution. This base resin layer coating solution is applied to the opposite surface of the base material provided with the hard coat layer using a bar coater count 16 manufactured by Matsuo Sangyo Co., Ltd. 1.2 J / cm ² irradiation and curing were performed, and a base resin layer having a coating thickness of 4.8 μm was provided.

Next, “conductive layer A” was laminated on the base resin layer with a gravure wire number 150R to obtain a conductive laminate of the present invention.

Example 12
Except having laminated | stacked the "electroconductive layer A" by the gravure wire number 100R, it produced similarly to Example 11 and obtained the conductive laminated body of this invention.

Example 13
On the “conductive layer A” of Example 6, a coating solution of “transparent protective layer material A” having a solid content concentration of 1.0 mass% was applied by microgravure coating (gravure wire number 80R, gravure rotation ratio 100%). The film was dried at 125 ° C. for 1 minute to provide a transparent protective layer having a thickness of 60 nm to obtain a conductive laminate of the present invention.

Example 14
On the “conductive layer A” of Example 6, a coating solution of “transparent protective layer material A” having a solid content concentration of 1.2 mass% was applied by microgravure coating (gravure wire number 80R, gravure rotation ratio 100%). The film was dried at 125 ° C. for 1 minute, and a transparent protective layer having a thickness of 75 nm was provided to obtain a conductive laminate of the present invention.

Example 15
On the “conductive layer A” of Example 6, a coating solution of “transparent protective layer material A” having a solid content concentration of 1.5 mass% was applied by microgravure coating (gravure wire number 80R, gravure rotation ratio 100%). The film was dried at 125 ° C. for 1 minute to provide a transparent protective layer having a thickness of 100 nm to obtain a conductive laminate of the present invention.

Example 16
A coating liquid of “transparent protective layer material B” having a solid content concentration of 1.5% by mass was applied by microgravure coating (gravure wire number 120R, gravure rotation ratio 100%) on “conductive layer A” of Example 6. After drying at 80 ° C. for 30 seconds, the film was cured by irradiation with ultraviolet rays of 1.2 J / cm ² to provide a transparent protective layer having a thickness of 65 nm to obtain a conductive laminate of the present invention.

Example 17
On the “conductive layer A” in Example 6, a coating solution of “transparent protective layer material B” having a solid content concentration of 1.5 mass% was applied by microgravure coating (gravure wire number 80R, gravure rotation ratio 100%). After drying at 80 ° C. for 30 seconds, the film was cured by irradiation with ultraviolet rays of 1.2 J / cm ² to provide a transparent protective layer having a thickness of 100 nm to obtain a conductive laminate of the present invention.

Comparative Example 1
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd., solid content concentration 82% by mass) on one side with a “film” having a thickness of 188 μm as a base material and a solid content concentration of 40: 1 with toluene / methyl ethyl ketone mass% ratio. A hard coating agent diluted to mass% is applied with a micro gravure coater (gravure wire number 80R, gravure rotation ratio 100%), dried at 80 ° C. for 1 minute, irradiated with ultraviolet rays at 1.0 J / cm ² and cured to a thickness of 5 μm. The hard coat layer was provided. Subsequently, it was set as the laminated body which does not provide a base resin layer and a conductive layer on the opposite surface which provided the hard-coat layer of the base material.

Comparative Example 2
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd., solid content concentration 82% by mass) on one side with a “film” having a thickness of 188 μm as a base material and a solid content concentration of 40: 1 with toluene / methyl ethyl ketone mass% ratio. A hard coating agent diluted to mass% is applied with a micro gravure coater (gravure wire number 80R, gravure rotation ratio 100%), dried at 80 ° C. for 1 minute, irradiated with ultraviolet rays at 1.0 J / cm ² and cured to a thickness of 5 μm. The hard coat layer was provided.

Next, 5.80 g of “resin A”, 0.174 g of “photopolymerization initiator” and 14.63 g of ethyl acetate were mixed and stirred to prepare a base resin layer coating solution. This base resin layer coating solution is applied to the opposite surface of the base material provided with the hard coat layer using a bar coater count 30 manufactured by Matsuo Sangyo Co., Ltd. 1.2 J / cm ^{2 was} irradiated and cured, and only a base resin layer having a coating thickness of 13 μm was provided, and a laminate without a conductive layer was obtained.

Comparative Example 3
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd., solid content concentration 82% by mass) on one side with a “film” having a thickness of 188 μm as a base material and a solid content concentration of 40: 1 with toluene / methyl ethyl ketone mass% ratio. A hard coating agent diluted to mass% is applied with a micro gravure coater (gravure wire number 80R, gravure rotation ratio 100%), dried at 80 ° C. for 1 minute, irradiated with ultraviolet rays at 1.0 J / cm ² and cured to a thickness of 5 μm. The hard coat layer was provided.

Next, the “conductive layer C” was directly laminated on the opposite surface of the base material on which the hard coat layer was provided, without providing the base resin layer, to obtain a conductive laminate.

Comparative Example 4
A conductive laminate was prepared in the same manner as in Comparative Example 3 except that the conductive layer was “conductive layer A” (laminated with gravure wire number 150R).

Comparative Example 5
A conductive laminate was prepared in the same manner as Comparative Example 3 except that the conductive layer was “conductive layer B”.

Comparative Example 6
Except that the resin used for the base resin layer coating solution was “resin C”, it was prepared in the same manner as in Example 1, and “conductive layer A” was formed on the base resin layer having a coating thickness after drying of 13 μm. No. 150R was laminated to obtain a conductive laminate.

Comparative Example 7
A conductive laminate was prepared in the same manner as Comparative Example 6 except that the “conductive layer A” to be laminated was laminated with the gravure wire number 100R.

Comparative Example 8
Except that the resin used for the base resin layer coating solution was “resin D”, it was prepared in the same manner as in Example 2, and “conductive layer A” was formed on the base resin layer having a coating thickness after drying of 13 μm. No. 150R was laminated to obtain a conductive laminate.

Comparative Example 9
Except that the resin used for the base resin layer coating solution was “resin E”, it was prepared in the same manner as in Example 28, and “conductive layer A” was formed on the base resin layer having a coating thickness after drying of 13 μm. No. 150R was laminated to obtain a conductive laminate.

Comparative Example 10
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd., solid content concentration 82% by mass) on one side with a “film” having a thickness of 188 μm as a base material and a solid content concentration of 40: 1 with toluene / methyl ethyl ketone mass% ratio. A hard coating agent diluted to mass% is applied with a micro gravure coater (gravure wire number 80R, gravure rotation ratio 100%), dried at 80 ° C. for 1 minute, irradiated with ultraviolet rays at 1.0 J / cm ² and cured to a thickness of 5 μm. The hard coat layer was provided.

Next, 1.00 g of “resin F”, 5.82 g of “resin B”, and 0.43 g of ethyl acetate were mixed and stirred to prepare a base resin layer coating solution. This base resin layer coating solution was applied to the opposite surface of the base material provided with the hard coat layer using a bar coater count 30 manufactured by Matsuo Sangyo Co., Ltd., and heated and dried at 100 ° C. for 3 minutes. A base resin layer having a coating thickness of 13 μm after drying was provided.

Next, “conductive layer A” was laminated on the base resin layer with a gravure wire number 150R to obtain a conductive laminate.

Comparative Example 11
KAYANOVA (registered trademark) FOP1740 (Nippon Kayaku Co., Ltd., solid content concentration 82% by mass) on one side with a “film” having a thickness of 188 μm as a base material and a solid content concentration of 40: 1 with toluene / methyl ethyl ketone mass% ratio. A hard coating agent diluted to mass% is applied with a micro gravure coater (gravure wire number 80R, gravure rotation ratio 100%), dried at 80 ° C. for 1 minute, irradiated with ultraviolet rays at 1.0 J / cm ² and cured to a thickness of 5 μm. The hard coat layer was provided.

Next, 1.00 g of “resin F”, 3.87 g of “resin G” and 2.46 g of ethyl acetate were mixed and stirred to prepare a base resin layer coating solution. This base resin layer coating solution is applied to the opposite surface of the base material provided with the hard coat layer using a bar coater count 30 manufactured by Matsuo Sangyo Co., Ltd., and dried by heating at 100 ° C. for 3 minutes. A base resin layer having a subsequent coating thickness of 13 μm was provided.

Next, an attempt was made to apply the carbon nanotube dispersion coating solution of “conductive layer A” onto the base resin layer, but it was repelled and the conductive layer could not be laminated.

In Examples 1 to 17, the writing quality and input sensitivity of the touch panel could be improved. In particular, a base resin layer in which a urethane acrylate having a specific structure of a glycol skeleton and a bifunctional acrylate moiety and a graft resin having a hydrophilic group in the side chain is used (Examples 1 to 4). 3, 6, 13-17) Not only was it possible to apply a water-dispersed coating liquid of the conductive component of the linear structure, but also the writing quality and input sensitivity were greatly improved. Furthermore, when the acrylate moiety of the urethane acrylate resin was bonded to another acrylate moiety (Examples 2, 6, 13 to 17), good durability could be obtained.

When the conductive layer is not provided (Comparative Examples 1 and 2), the touch panel does not work. When no base resin layer was provided (Comparative Examples 3 to 5), the writing quality and input sensitivity were poor. When the skeleton structure of the urethane acrylate resin in the base resin layer is not a glycol skeleton (Comparative Examples 6 and 7), or when it is a glycol skeleton but not a urethane acrylate (Comparative Examples 8, 9, and 10), Input sensitivity has deteriorated. Furthermore, when the side chain of the graft resin was a hydrophobic group, the aqueous dispersion coating solution could not be applied and the conductive layer could not be laminated (Comparative Example 11).

The present invention is a conductive laminate having good touch panel writing, high input sensitivity, and good durability. Furthermore, it is an electroconductive laminated body used also for electrode members used, such as a liquid crystal display, organic electroluminescence, electronic paper related display, and a solar cell module.

1: base material 2: base resin layer 3: conductive layer 4: transparent protective layer 5: backbone polymer 6 of main chain: branched side chain 7: hydrophilic group 8: conductive surface 9 observed from a direction perpendicular to the laminated surface: Example of carbon nanotube (example of line structure)
10: An example of a nanowire of metal or metal oxide (an example of a linear structure)
11: Example of metal oxide whisker or fibrous needle-like crystal (an example of a linear structure)
12: Conductive thin film 13: Upper electrode 14: Lower electrode 15: Upper electrode substrate 16: Lower electrode substrate 17: Hard coat layer 18: Dot spacer 19: Double-sided adhesive tape 20: Space 21: Power supply 22: Pen DESCRIPTION OF SYMBOLS 100: Reactor 101: Quartz sintered board 102: Sealed catalyst supply machine 103: Catalyst injection line 104: Raw material gas supply line 105: Exhaust gas line 106: Heater 107: Inspection port 108: Catalyst

Claims (12)

1. A conductive laminate in which a base resin layer and a conductive layer are laminated in order of a base resin layer and a conductive layer from at least one side of the base material in the order of the base resin layer, and the base resin is a urethane acrylate resin having a glycol skeleton; A conductive laminate, which is a resin containing a graft structure resin having a hydrophilic group in a side chain.
2. The conductive laminate according to claim 1, wherein the conductive layer contains carbon nanotubes.
3. The conductive laminate according to claim 1, wherein the glycol skeleton is a polyethylene glycol skeleton and / or a polypropylene glycol skeleton.
4. The conductive laminate according to claim 1, wherein the urethane acrylate resin is a urethane acrylate resin in which the number of functional groups at the acrylate moiety in one molecule of urethane acrylate is bifunctional.
5. The conductive laminate according to claim 1, wherein an acrylate moiety of the urethane acrylate resin is bonded to another acrylate moiety by polymerization.
6. The ratio t / T between the thickness T of the substrate and the thickness t of the base resin layer is
   0.040 ≦ t / T ≦ 0.080
   The conductive laminate according to claim 1, wherein
7. The conductive laminate according to claim 1, wherein the total light transmittance based on JIS K7361-1 (1997) when incident from the conductive layer side is 80% or more.
8. The conductive laminate according to claim 1, wherein the substrate is a transparent substrate.
9. A method for producing a conductive laminate in which a base resin layer is formed on a substrate and then a conductive layer is formed on the base resin layer, wherein the base resin has a glycol skeleton with a urethane acrylate resin and a hydrophilic group in a side chain. The manufacturing method of the electrically conductive laminated body containing resin of the graft structure which has this.
10. The method for producing a conductive laminate according to claim 9, wherein the conductive layer is formed by applying a water-containing dispersion of carbon nanotubes or silver nanowires and then drying.
11. The manufacturing method of the conductive laminated body of Claim 11 which forms a protective layer on a conductive layer.
12. A touch panel using the conductive laminate according to any one of claims 1 to 8.

Images